Tricyclo[3.3.2.0 4, 6]decadiene-2, 7-one-10 and process therefor



United States Patent 3,403,182 TRICYCLO[3.3.2.0 ]DECADIENE-2,7-0NE-10AND PROCESS THEREFOR Jan Nielsen and Cornelis Hoogzand, Brussels,Belgium, assignors to Union Carbide Corporation, a corporation of NewYork No Drawing. Filed May 25, 1965, Ser. No. 458,774 2 Claims. (Cl.260-586) ABSTRACT OF THE DISCLOSURE Tricycl-o[3.3.2.0decadienc-2,7-one-10 is prepared by contacting [N-methyl N(beta-N,N'-dimethylaminoethyl)]tricyclo[3.3.2.0 ]deca-2,7,9'-triene withsilica gel. The ketone is useful as a polar solvent which is liquid overa wide range of temperature.

This invention relates to polycyclic organic compounds. Moreparticularly the invention is directed to tricyclo[3.3.2.0decadiene-ZJ-one-IO, derivatives there- -of and a process for producingthe compound and derivatives.

.The compound tricyclo[3.32.0 ]deca-2,7,9'-triene and many of itsderivatives are known and described in the literature.

The structural formula for tricyclo[3.3.2.0 ]deca- 2,7,9-triene, C H isas follows:

The structural formula for tricyclo[3.3.2.O decadiene-2,7-one-10, C H O,is as follows:

It has now been discovered that the ketone derivative oftricyclo[3.3.2.02 ]deca-2,7,9-triene exists and can be prepared by theprocess which comprises contacting a secondary-amino derivative of thecompound of Formula A with silica gel. This is conveniently done bypassing an organic solvent solution of the secondary-amino derivative ofthe compound of formula A through a column containing silica gel. Aconventional column chromatography apparatus is satisfactory.

The alkylamino derivative of the compound of Formula A can in turn beprepared by the reaction of the mono- 'bromo derivative ofthe compoundof Formula A with an alkali metal derivative of a secondary amine.

Derivatives of the compound of Formula B, for example the alkyl, aryl,alkenyl, alkoxy, alkoxyalkyl, and the like derivatives, can be prepared(conveniently starting with the corresponding mono-bromo derivatives ofthe compound of Formula A) from the corresponding secondaryamino-derivatives of the compound of Formula A.

The compound of Formula B exists in equilibrium with the correspondingenol form represented by the formula The equilibrium greatly favors theketo form of Formula B.

G. Schroder, R. Merenyl and J. F. M. 0th, Tetrahedron Letters No. 14,773, 1964.

3,403,182 Patented Sept. 24, 1968 can be epoxidized to give compoundswhich are useful as stabilizers for various resin systems. Additionally,many of the unsaturated polycyclic compounds are relatively re activematerials which homopolymerize or copolymerize readily with otherreactive cyclic monomers to provide a useful class of polymericcompounds. These polymers can range from viscous liquids to extremelytough solids. The very viscous liquids of relatively low molecularweight, are useful in the preparation of polishes, and waxes, and asthickening agents for various lubricants. The polymers can be employedas protective coatings and impregnants. These polymers are also usefulfor the production of various shaped articles such as brush handles,bottoms, lamp bases, toys and the like.

The compound of Formula B is also useful as a polar solvent for chemicalreactions, particularly where a polar solvent which is liquid over awide range of temperature is desired.

The following detailed example further illustrates the presentinvention. 100 ml. of a 2 N solution of CH Li in diethyl ether areslowly added with stirring to 25 ml. of

To this solution is added 5.0 g. of bromobullvalene (CH H Br) dissolvedin 50 ml. of

G. Schroder, R. Mereuyi and .T. F. M. 01:11, Tetrahedron Letters No. 14,773 (1964).

and the mixture stirred at 30 C. for 18 hours. To the resultant brownreaction product, 100 ml. of water are slowly added with stirring. Thesolution is then extracted with 50 ml. pentane. The pentane extract isremoved and the extraction process repeated twice, each time using 50ml. of pentane. The combined pentane extract fractions were driedovernight using 5 g. of Na SO The pentane was then evaporated (40 mm./50C.) and the residue oil, 4.84 g., distilled in a molecular still under apressure of 0.01 mm. at C. 4.2. g. of

N CH

-CH CH N 3Z 2 were obtained.

The above intermediate product is dissolved in 10 ml. of benzene and thesolution passed over a column (50 cm. high, 25 cm. diameter) of silicagel at room temperature. Hydrolysis of the above intermediate productoccurs during elution with additional benzene (500- ml.) yielding theproduct 4 t-ricycl0[3.3.2.0 ]decadiene-2,7-one-1O andIO-hydroxytricyclo[3.3.2.0 ]deca-2,7,9-triene which comprises contacting[N-methyl-N-(beta-N',N'-dimethylaminoethyl) tricyclo 3.3.2.0deca-2,7,9-triene,

with silica gel.

References Cited Raphael et 211.: Adv. in Org. Chem, vol. 3, pp. 260-261 (196-3). f 7 Schroder: Chem. Ber., vol. 97(11), p. 3143 (1964).

adiene-2,7-one-l0 and IO-hydroxytricyclo[3.3.2.0 ]deca- 20 BERNARDHELFIN Primary Examinen 2,7,9-triene.

2. The process for producing the keto-enol mixture of M. JACOB,Assistant Examiner.

